KR20090046883A - Curable resin composition and method for forming cured coating film - Google Patents

Abstract

Curable resin composition of this invention is a copolymer containing the monomer unit (A) containing an alkali-soluble group, and the monomer unit (B) corresponding to a curable group containing polymeric unsaturated compound, The ratio of the said monomer unit (B) is air 5 to 95% by weight relative to the total monomer units constituting the copolymer, wherein at least 30% by weight of the monomer unit (B) is selected from 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compounds The copolymer which is a monomeric unit corresponding to a compound of a kind or more, and the organic solvent whose boiling point at normal pressure are 180 degreeC or more are included. According to such a curable resin composition, the film which is excellent in transparency, heat resistance, etc. can be formed, and especially when it coats by the slit coating method or the inkjet method, the thickness of a coating film does not differ partially or a coating film defect does not arise.

Alkali-soluble group, curable group containing, polymerizable unsaturated compound, slit coating method, inkjet method

Description

Formation method of curable resin composition and cured coating film {CURABLE RESIN COMPOSITION AND METHOD FOR FORMING CURED COATING FILM}

The present invention relates to a curable resin composition comprising a copolymer having a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring and a method of forming a cured coating film using the same. More specifically, lithography using active rays such as far ultraviolet rays, electron beams, ion beams, X-rays, semiconductors, insulating films, protective films, and the like provided in electronic components such as liquid crystal display devices, integrated circuit devices, and solid-state imaging devices may be used. It relates to the curable resin composition used for forming and the formation method of the cured coating film using the same.

In general, in the field of manufacturing various electronic devices requiring submicron-level microfabrication, which is represented by VLSI, there is an increasing demand for additional high density and high integration of devices. For this reason, the demand for photolithography technology, which is a fine pattern formation method, is becoming more and more strict. On the other hand, in electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements, a protective film for preventing its deterioration or damage, an interlayer insulating film provided to insulate between wirings arranged in layers, and for flattening the element surface. A planarization film and an insulation film for maintaining electrical insulation are provided. Above all, in the case of a liquid crystal display element, for example, a TFT type liquid crystal display element is provided with a polarizing plate on a glass substrate, forms a transparent conductive circuit layer such as ITO and a thin film transistor (TFT), and is coated with an interlayer insulating film to form a back surface. On the other hand, a polarizing plate is provided on a glass plate, the pattern of a black matrix layer and a color filter layer is formed as needed, and a transparent conductive circuit layer and an interlayer insulation film are formed sequentially, and it is set as a top plate, and this back plate And the top plate to face each other with a spacer therebetween and the liquid crystal is enclosed between the two plates, and the photosensitive resin composition used herein should be excellent in transparency, heat resistance, developability and flatness.

As a highly sensitive method of resists, chemically amplified resists using photoacid generators as photosensitizers are well known. For example, using a curable resin composition containing a resin containing a structural unit having an epoxy group and a photoacid generator, a proton is generated from the photoacid generator by exposure, and the epoxy group is cleaved to cause a crosslinking reaction. As a result, the resin becomes insoluble in the developing solution, a pattern is formed, and the resist solid phase is moved by the heat treatment after exposure, and the acid chemically amplifies chemical changes such as the resist resin. In this manner, a significant increase in sensitivity is achieved as compared with a conventional resist having a photoreaction efficiency (reaction per photon) of less than one. Currently, most of the resists to be developed are chemically amplified, and the use of chemical amplification mechanisms is essential for the development of highly sensitive materials corresponding to shortening of the exposure light source.

On the other hand, since fine processing is necessary for the insulating film provided in a TFT type liquid crystal display element or an integrated circuit element, a radiation sensitive resin composition is generally used as a material for forming this insulating film, and such a radiation sensitive resin The composition is required to have high radiation sensitivity in order to obtain high productivity. In addition, when the insulating film has low solvent resistance, swelling, deformation, peeling from the substrate, or the like occurs due to the organic solvent on the insulating film, which causes serious obstacles in the manufacture of the liquid crystal display element and the integrated circuit element. For this reason, excellent solvent resistance is calculated | required by such an insulating film. Moreover, high transparency is required for the insulating film provided in a liquid crystal display element, a solid-state image sensor, etc. as needed.

In such a request, Japanese Patent Laid-Open No. 2003-76012 discloses a photosensitive resin composition comprising a copolymer of an alicyclic epoxy group-containing polymerizable unsaturated compound and a radical polymerizable compound, and is an unsaturated carbon as a radical polymerizable compound. Acids and the like are used. In the optically amplified resist, the epoxy compound is easily crosslinked by an acid generated by the photoacid generator and subsequent heating (post-baking), and is effective for obtaining a film having good etching resistance. However, while the alicyclic epoxy group-containing polymerizable unsaturated compound is rich in cationic polymerizability, it is easy to react with the carboxyl group derived from unsaturated carboxylic acid used for imparting alkali solubility, and because of poor storage stability, it is -20 ° C or less. There is a big problem in practicality because it is necessary to preserve | save at low temperature.

Further, Japanese Patent No. 3055495 discloses a monomer unit corresponding to a (meth) acrylic acid ester in which a cross-linkable hydrocarbon group is directly bonded to an oxygen atom of an ester, a monomer unit having an epoxy-containing hydrocarbon group, and a monomer unit having a carboxyl group. A photosensitive resin composition comprising a copolymer is disclosed. However, the (meth) acrylic acid ester in which the cross-linkable hydrocarbon group is directly bonded to the oxygen atom of the ester has a very bulky group in the adjacent position of the ester group, and thus, monomer synthesis is often difficult and poorly soluble in an organic solvent. , The polymerization reaction and handling of the obtained resin are difficult. In addition, the (meth) acrylic acid ester in which a cross-linkable hydrocarbon group is directly bonded to the oxygen atom of the ester has a very low polarity, and thus, when copolymerized with a highly polar unsaturated carboxylic acid or an epoxy group-containing monomer, the monomer composition of the polymer is biased. The polymer of a uniform composition is not obtained and therefore a desired resist performance is not obtained.

On the other hand, various solvents are used as solvents for dissolving curable resins having curable groups such as epoxy groups. However, as solvents excellent in various properties such as solubility, coating properties, sensitivity, developability, and pattern characteristics to be formed, ethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are known.

Moreover, as a method of apply | coating the curable resin composition which melt | dissolved curable resin in the solvent on a board | substrate or a base material, although the spin coating method, the roll coating method, and the spraying method have conventionally been used widely, in recent years, the coating liquid use rate improvement, process shortening, etc. In view of the excellent surface, the coating film is formed by the slit coating method or the inkjet method. However, according to the investigation by the present inventors, when forming a coating film by the slit method or the inkjet method, depending on the kind of resin, the thickness of a coating film may differ partially or a coating film defect may arise.

Patent Document 1: Japanese Patent Laid-Open No. 2003-76012

Patent Document 2: Japanese Patent No. 3055495

<Start of invention>

Problems to be Solved by the Invention

An object of the present invention is to form a film (cured coating film) having excellent properties such as hardness, transparency, heat resistance, and heat discoloration resistance, and excellent storage stability, and in particular, when coating by a slit coating method or an inkjet method. It is providing the curable resin composition in which the thickness of a coating film differs or a coating film defect does not arise, and the formation method of a cured coating film.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM The present inventors discovered the following content as a result of earnestly examining in order to achieve the said objective. That is, as a result of examining the polymer which can form the film which is excellent in solvent solubility, the storage stability of a solution is very good, and also excellent in transparency, heat resistance, etching resistance, flatness, developability, etc., it has an alkali-soluble group. It has been found that the polymer obtained by copolymerizing a polymerizable unsaturated compound with a monomer mixture comprising a polymerizable unsaturated compound containing a specific amount of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring has excellent properties. . However, the polymer is dissolved in propylene glycol monomethyl ether or the like, which is generally considered to be excellent as a solvent for the photosensitive resin, to prepare a curable resin composition, which is coated on a substrate or a substrate by a slit coating method or an inkjet method, and cured to form a film. When the film was formed, there was a problem that the thickness of the coating film was partially different or the coating defect occurred. As a result of the investigation in order to find a solvent in which such a problem does not occur, it was found that a specific organic solvent is very effective when the curable resin composition is applied, in particular, by using the slit coating method or the inkjet method. The present invention has been completed based on these contents.

That is, this invention is a copolymer containing the monomeric unit (A) containing an alkali-soluble group, and the monomeric unit (B) corresponding to a curable group containing polymeric unsaturated compound, The ratio of the said monomeric unit (B) makes a copolymer 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane, which is 5 to 95% by weight relative to the total monomer units constituting, and at least 30% by weight of the monomer units (B) are represented by the following general formulas (1a) and (1b). It provides the curable resin composition containing the copolymer which is a monomer unit corresponding to at least 1 sort (s) of compound selected from a ring containing compound, and the organic solvent whose boiling point at normal pressure is 180 degreeC or more.

(Wherein R ^a represents an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, respectively, and A represents a divalent hydrocarbon group which may each include a single bond or a hetero atom)

The copolymer is in addition to the monomer units (A) and (B), (C) (c1) a styrene which may be substituted with an alkyl group, (c2) an unsaturated carboxylic ester represented by the following formula (2), and (c3) And monomer units corresponding to at least one curable group-free polymerizable unsaturated compound selected from the group consisting of N-substituted maleimides.

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ² represents a primary or secondary alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group, an aralkyl group, or- (R ³ -O) represents an _m -R ⁴ group, wherein R ³ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or more.

The 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compound represented by Formula 1a or 1b may be a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) Acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9 -Yloxy) ethyl (meth) acrylate, or 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate.

As the organic solvent, not less than the boiling point at normal pressure of 180 ℃, C _{5 -6} cycloalkane diols, C _{5 -6} cycloalkanediyl methanol, C _{5 -6} cycloalkane diol mono- or di-acetate, C _{5 -6} cycloalkanediyl mono methanol or di-acetate, propylene glycol mono or diallyl ether, dipropylene glycol mono-C _{1 -4} alkyl ether, dipropylene glycol C _{2 -4-alkyl} ether, dipropylene glycol mono-C _{1 -4} alkyl ether acetate, tripropylene glycol monomethyl or di-C _1-4 alkyl ethers, propylene glycol diacetate, 1,3-propanediol di-C _{3 -4} alkyl ethers, 1,3-propanediol mono-C _{2 -4} alkyl ether acetates, 1,3-propanediol mono or diacetate, 1,3-butanediol mono- or di-C _{3 -4} alkyl ether, 1,3-butanediol mono C _{2 -4} alkyl ether acetates, 1,3-butanediol mono- or diacetate, 1,4-butanediol mono- or D C _{3 -4} alkyl ether, 1,4-butanediol mono C _{2 -4} alkyl ether acetates, 1,4-butanediol mono- or diacetate, glycerol mono-, di- or tri- C _{1 -4} alkyl ethers, glycerol mono-, di- or triacetate, glycerol mono- or di-C _{1 -4} alkyl ether di- or mono-acetate, 3,5,5-trimethyl-2-cyclohexen-1-one, diethylene glycol mono-C _{2 -4} alkyl ether, and diethylene glycol mono-C ₂ One or more organic solvents selected from _-4 alkyl ether acetates can be used.

The present invention also provides a method of forming a cured coating film wherein the curable resin composition is coated on a substrate or a substrate by a slit coating method or an inkjet method to form a coating film and then the coating film is cured.

Effect of the Invention

According to the present invention, it is possible to form a film (cured coating film) having excellent properties such as hardness, transparency, heat resistance, heat discoloration resistance, and at the same time, excellent in storage stability, and particularly in the case of coating by the slit coating method or the inkjet method. Therefore, there is no problem that the thickness of the coating film is different or the coating film defect occurs.

Best Mode for Carrying Out the Invention

[Copolymer]

The copolymer contained in curable resin composition of this invention contains the monomeric unit (A) containing an alkali-soluble group, and the monomeric unit (B) corresponding to a curable group containing polymeric unsaturated compound. The monomer unit (A) containing an alkali-soluble group has a function etc. which impart alkali solubility to a polymer (copolymer). Thereby, a polymer is melt | dissolved in aqueous alkali solution (developer) at the time of image development. In addition, the monomer unit (B) has a function of curing the polymer in the presence of heat or light to impart the necessary hardness to the coating.

The monomer unit (A) containing an alkali soluble group can be introduced into the polymer by copolymerizing a polymerizable unsaturated compound (a) having an alkali soluble group. As said alkali-soluble group, what is necessary is just a group normally used in the resist field, For example, a carboxyl group, a phenolic hydroxyl group, etc. are mentioned. Typical examples of the polymerizable unsaturated compound (a) having an alkali-soluble group include unsaturated carboxylic acids or acid anhydrides, hydroxystyrenes or derivatives thereof, but are not limited thereto. Among these, especially unsaturated carboxylic acid or its acid anhydride is preferable.

As unsaturated carboxylic acid or its acid anhydride, for example, α, β-unsaturated carboxylic acid and its acid anhydride such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and the like (Maleic anhydride, itaconic anhydride, etc.) are illustrated. Among these, acrylic acid and methacrylic acid are particularly preferable. The polymerizable unsaturated compound (a) which has an alkali-soluble group can be used individually or in combination of 2 or more.

Although the ratio which occupies in the copolymer of the monomeric unit (A) containing alkali-soluble group differs according to the kind of monomer to be used and the type of resist (negative type or positive type), it is usually with respect to the whole monomeric unit which comprises a copolymer. It is 10-50 weight%, Preferably it is 12-40 weight%, More preferably, it is 14-30 weight%. If the ratio is too small, it is difficult to dissolve in the alkaline developer, leading to poor developability. On the contrary, too large, the etching resistance after development deteriorates, which is not preferable.

The monomer unit (B) corresponding to the curable group-containing polymerizable unsaturated compound is reacted with a crosslinking agent using a crosslinking agent at the time of exposure or the like with a alkali-soluble group (eg, carboxyl group, phenolic hydroxyl group, etc.) in the polymer molecule. Thereby curing the polymer, imparting the necessary hardness as a resist to the film, thereby increasing the etching resistance, and also the function of changing the polymer to alkali insolubility.

The monomeric unit (B) corresponding to a curable group containing polymeric unsaturated compound can be introduce | transduced into a polymer by copolymerizing a curable group containing polymeric unsaturated compound (b). As the curable group-containing polymerizable unsaturated compound (b), a compound having a group having a polycyclic aliphatic group having an epoxy group on the ring and having an unsaturated bond is preferable. A dicyclopentanyl group, a tricyclodecyl group, etc. are mentioned as said polycyclic aliphatic group. A carbon-carbon double bond is mentioned as said unsaturated bond, A vinyl group, an allyl group, a metalyl group, acryloyl group, a methacryloyl group etc. are mentioned as a group which has an unsaturated bond.

In the present invention, as the curable group-containing polymerizable unsaturated compound (b), at least one compound selected from 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compounds represented by the general formulas (1a) and (1b) is used. . In Formulas 1a and 1b, R ^a represents an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, respectively, and A represents a divalent hydrocarbon group that may each include a single bond or a hetero atom.

Examples of the alkyl group having 1 to 7 carbon atoms that may be substituted with ^a hydroxyl group at R ^a include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, heptyl, and the like. ; Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy And hydroxyalkyl groups such as hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, and 4-hydroxybutyl group. As R ^a, an alkyl group having 1 to 2 carbon atoms which may be substituted with ^a hydrogen atom or a hydroxyl group is preferable, and a hydrogen atom or a methyl group is particularly preferable.

In a divalent hydrocarbon group which may include a hetero atom at A, the hetero atom may be bonded to the end of the hydrocarbon group and may be interposed between the carbon atoms constituting the hydrocarbon group. Nitrogen, oxygen, a sulfur atom, etc. are mentioned as a hetero atom.

As a representative example of A, the group represented by following formula (3) is mentioned.

(Wherein R ⁵ represents a divalent hydrocarbon group having 1 to 12 carbon atoms and n represents an integer of 0 or more)

As a C1-C12 bivalent hydrocarbon group in R <^5> , For example, bivalent linear form, such as methylene, ethylene, propylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene group, or Branched alkylene groups; Divalent alicyclic hydrocarbon groups (cycloalkylene group, cycloalkylidene group, divalent crosslinked carbocyclic group, etc.) such as cyclopentylene, cyclohexylene, cyclopentylidene and cyclohexylidene; The divalent hydrocarbon group etc. to which these were couple | bonded two or more are mentioned. As R <^5> , In particular, C1-C6 alkylene groups, such as methylene, ethylene, propylene, tetramethylene, hexamethylene group; 3-6 membered alicyclic hydrocarbon groups, such as a cyclohexylene group, etc. are preferable. As n, Preferably it is an integer of 0-10, More preferably, it is an integer of 0-4, Especially preferably, it is 0 or 1.

As another representative example of A, Alkylene group (for example, C1-C12 alkylene group, especially C1-C6 alkylene group), such as a methylene group, ethylene group, a propylene group, trimethylene group; Thioalkylene groups (for example, thioalkylene groups having 1 to 12 carbon atoms, especially thioalkylene groups having 1 to 6 carbon atoms) such as thiomethylene groups, thioethylene groups, and thiopropylene groups; Amino alkylene groups (for example, C1-C12 aminoalkylene group, especially C1-C6 aminoalkylene group), such as an amino methylene group, an aminoethylene group, and an aminopropylene group, etc. are mentioned.

A is preferably a single bond [when n is 0 in Formula 3], an alkylene group having 1 to 6 carbon atoms (especially 1 to 3 carbon atoms), an oxyalkylene group having 1 to 6 carbon atoms (especially 2 to 3 carbon atoms) [ in the above formula (3) wherein n is 1, R ⁵ is a group] C _{1 -6} alkylene group (particularly C _2-3 alkylene group), more preferably single bond or oxyethylene group.

As a representative example of the 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compound represented by the formulas (1a) and (1b), an epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo] [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate; 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytrityl] Cyclo [5.2.1.0 ^2,6 ] decane-9-yloxy) ethyl (meth) acrylate; 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate], epoxidized dicyclopentenyloxybutyl (meth) acrylate, epoxidized dish Clopentenyloxyhexyl (meth) acrylate etc. are mentioned. Especially, epoxidized dicyclopentenyl (meth) acrylate and epoxidized dicyclopentenyl oxyethyl (meth) acrylate are especially preferable.

The compound represented by the formula (1a) and the compound represented by the formula (1b) may each be used alone. In addition, these can be mixed and used in arbitrary ratios. When the mixture is used in combination, the ratio is preferably Formula 1a: Formula 1b = 5: 95 to 95: 5, more preferably 10:90 to 90:10, and more preferably 20:80 to 80: 20.

In the present invention, a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compound represented by the general formulas (1a) and (1b) and other curable group-containing polymerizable unsaturated compounds (hereinafter referred to as "other curable group containing May be referred to as a "polymerizable unsaturated compound". Other curable group-containing polymerizable unsaturated compounds may be, for example, oxiranyl (meth) acrylate, glycidyl (meth) acrylate, or 2- Methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-oxyranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycid Polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives) containing an oxirane ring (monocyclic) such as dioxypropyl (meth) acrylate and glycidyloxyphenyl (meth) acrylate; 3,4-epoxycyclo Hexyl (meth) acrylate, 3,4-epoxycyclohexylme (Meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3,4-epoxycyclohexylmethyloxy) ethyl (meth) acrylate, 3- (3,4 -Polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives) containing an epoxy group-containing alicyclic carbocyclic ring such as 3,4-epoxycyclohexane ring such as epoxycyclohexylmethyloxy) propyl (meth) acrylate; Polymerizable unsaturated compound ((meth) acrylic acid containing 5,6-epoxy-2-bicyclo [2.2.1] heptane ring, such as 6-epoxy-2- bicyclo [2.2.1] heptyl (meth) acrylate Ester derivatives); and the like.

Moreover, as another curable group containing polymeric unsaturated compound, For example, oxetanyl (meth) acrylate, 3-methyl-3- oxetanyl (meth) acrylate, 3-ethyl-3- oxetanyl (meth) ) Acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, 2- (3-methyl-3-jade Cetanyl) ethyl (meth) acrylate, 2- (3-ethyl-3-oxetanyl) ethyl (meth) acrylate, 2-[(3-methyl-3-oxetanyl) methyloxy] ethyl (meth ) Acrylate, 2-[(3-ethyl-3-oxetanyl) methyloxy] ethyl (meth) acrylate, 3-[(3-methyl-3-oxetanyl) methyloxy] propyl (meth) Oxetane ring-containing polymerizable unsaturated compounds such as acrylate and 3-[(3-ethyl-3-oxetanyl) methyloxy] propyl (meth) acrylate; Oxolane ring containing polymeric unsaturated compounds, such as tetrahydrofurfuryl (meth) acrylate, etc. are mentioned. As another curable group containing polymerizable unsaturated compound, the allyl ether allyl ether containing an oxirane ring, an oxetane ring, or an oxolane ring, a vinyl ether compound, an oxirane ring, an oxetane ring, or an oxolane ring can also be used.

The proportion of the copolymer of the monomer unit (B) corresponding to the curable group-containing polymerizable unsaturated compound is in the range of 5 to 95% by weight, preferably 40 to 90% by weight, more preferably 45 to 1% based on the total monomer units. 85 wt%. When this ratio is less than 5 weight%, the crosslinking reaction at the time of exposure does not fully advance, and heat resistance and etching resistance will fall. On the other hand, when the said ratio exceeds 95 weight%, characteristics, such as alkali solubility, will become inadequate and a favorable pattern will not be formed.

In the present invention, the 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compound represented by the above formulas (1a) and (1b) in the monomer unit (B) corresponding to the curable group-containing polymerizable unsaturated compound The proportion of monomer units corresponding to the total is 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more. When this ratio is less than 30 weight%, when using together with the polymerizable unsaturated compound containing an epoxy-group containing alicyclic carbocyclic ring, storage stability will worsen, and the polymerizable unsaturated compound containing an oxirane ring (monocyclic), for example. When used in combination with (glycidyl group-containing monomer, etc.), the performance required for the radiation-sensitive resin, such as insufficient heat resistance, becomes insufficient.

In the present invention, the copolymer is in addition to the monomer units (A) and (B), (C) (c1) styrene which may be substituted with an alkyl group, (c2) unsaturated carboxylic acid ester represented by the formula (2), and ( c3) a monomer unit corresponding to at least one curable group-free polymerizable unsaturated compound selected from the group consisting of N-substituted maleimides. In formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ² represents a primary or secondary alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group, an aralkyl group, or- (R ³ -O) represents an _m -R ⁴ group (wherein R ³ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or more). The monomer unit (C) has a function of imparting the hardness required as a resist or the like to the film. In addition, the corresponding monomer may have a function of facilitating the copolymerization reaction. Moreover, it also has a function which raises the hardness of a film by crosslinking reaction etc. depending on the kind.

Examples of the alkyl group of styrene (c1) which may be substituted with an alkyl group include alkyl groups having 1 to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and hexyl groups. have. Among these, alkyl groups having 1 to 4 carbon atoms such as a methyl group or an ethyl group are preferable, and a methyl group is particularly preferable. The alkyl group may be bonded to any of the vinyl group and the benzene ring of styrene. Representative examples of styrene (c1) which may be substituted with an alkyl group include styrene, α-methylstyrene, vinyltoluene (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene) and the like. These can be used individually or in combination of 2 or more types.

Examples of the alkyl group having 1 to 7 carbon atoms in R ¹ of the unsaturated carboxylic acid ester (c2) represented by the formula (2) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, hexyl group Etc. can be mentioned. As R ¹ , a hydrogen atom or a methyl group is particularly preferable.

As a C1-C12 primary or secondary alkyl group in R <^2> , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, hexyl, octyl, decyl, dodecyl group, etc. are mentioned, for example. Can be. Examples of the alkenyl group having 2 to 12 carbon atoms include primary or secondary alkenyl groups such as allyl, 3-butenyl and 5-hexenyl groups. A phenyl group etc. are mentioned as an aryl group. A benzyl group etc. are mentioned as an aralkyl group.

In the ^{R 2 - (R 3 -O)} m -R ^4, of the groups, R ³ is a group, a divalent hydrocarbon group having 1 to 12 R ⁴ represents a hydrogen atom or a hydrocarbon group, m is 1 or more integer. As said C1-C12 bivalent hydrocarbon group, the thing similar to the C1-C12 bivalent hydrocarbon group in said R <^5> is mentioned. Especially, C2-C6 alkylene groups, such as ethylene, propylene, tetramethylene, and a hexamethylene group; 3-6 membered alicyclic hydrocarbon groups, such as a cyclohexylene group, etc. are preferable. Hydrocarbon group in R ⁴ includes, for the aliphatic hydrocarbon group such as an alkyl group (e.g. C _{1 -6} alkyl group, etc.), such as methyl, ethyl, propyl, isopropyl, butyl, hexyl; Alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups, and crosslinked carbocyclic groups such as norbornyl groups (bicyclo [2.2.1] heptyl groups) and tricyclo [5.2.1.0 ^2,6 ] decyl groups ; And groups in which two or more of them are bonded. As m, Preferably it is an integer of 1-10, More preferably, it is an integer of 1-4, Especially preferably, it is 1.

As a representative example of the unsaturated carboxylic acid ester (c2) represented by the formula (2), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth ) Acrylate, allyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- ( Tricyclo [5.2.1.0 ^2,6 ] decyloxy) ethyl (meth) acrylate; and the like. Unsaturated carboxylic acid ester (c2) represented by General formula (2) can be used individually or in combination of 2 or more types.

As N-substituted maleimide (c3), the compound etc. which are represented by following formula (4) can be used.

[Wherein, R ⁶ represents an organic group]

The organic group includes a hydrocarbon group and a heterocyclic group. Aliphatic hydrocarbon groups such as hydrocarbon group, for example methyl, ethyl, propyl, isopropyl, butyl, (such as for example C _{1 -6} alkyl group), alkyl groups such as hexyl group; Alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cyclooctyl group, and crosslinked carbocyclic groups such as adamantyl group and norbornyl group; Aryl groups such as phenyl group; Aralkyl groups such as benzyl group; The group etc. to which these were couple | bonded two or more are mentioned. As a heterocyclic group, about 5-10 membered non-aromatic or aromatic heterocyclic group containing 1 or more types of hetero atoms selected from the group which consists of a nitrogen atom, an oxygen atom, and a sulfur atom is mentioned, for example.

As a typical example of N-substituted maleimide (c3), For example, N-cycloalkyl maleimide, such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-cyclooctyl maleimide; N-crosslinked carbocyclic group-substituted maleimides such as N-adamantyl maleimide and N-norbornyl maleimide; N-alkyl maleimides such as N-methyl maleimide, N-ethyl maleimide and N-propyl maleimide; N-aryl maleimide, such as N-phenyl maleimide; N-aralkyl maleimide, such as N-benzyl maleimide, etc. are mentioned. Among these, N-cycloalkyl maleimide, such as N-cyclohexyl maleimide, N-crosslinked carbocyclic group substituted maleimide, etc. are preferable. N-substituted maleimide (c3) can be used individually or in combination of 2 or more types.

The copolymer of the present invention may contain a small amount of other monomer units in addition to the monomer unit (A), the monomer unit (B) and the monomer unit (C). As said monomeric unit, the unit corresponding to (meth) acrylamide, (meth) acrylonitrile, etc. are mentioned, for example. When the copolymer of the present invention contains a monomer unit (A) and a monomer unit (B) and does not include a monomer unit (C), the total amount of the monomer unit (A) and the monomer unit (B) It is 98 weight% or more normally, Preferably it is 99 weight% or more, More preferably, it is substantially 100 weight%. In addition, when the copolymer of this invention contains a monomeric unit (A), a monomeric unit (B), and a monomeric unit (C), the total amount of these 3 types of monomeric units is 90 weight based on all monomeric units, for example. It is preferably at least 95%, preferably at least 95% by weight, more preferably at least 98% by weight, and particularly preferably at most 100% by weight.

The copolymer of the present invention is a monomer mixture containing the polymerizable unsaturated compound (a) having the alkali-soluble group and the curable group-containing polymerizable unsaturated compound (b), and the ratio of the curable group-containing polymerizable unsaturated compound (b) is 3,4-epoxycitcyclo [5. 5 to 95% by weight relative to the total amount of monomers, and at least 30% by weight of the curable group-containing polymerizable unsaturated compound (b) represented by the general formulas (1a) and / or (1b). 1.0 ^2,6 ] can be manufactured by copolymerizing the monomer mixture which is a decane ring containing compound.

As a polymerization initiator used for copolymerization, a normal radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), diethyl-2,2'-azo Azo compounds such as bis (2-methylpropionate) and dibutyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide and t-butylperoxy pivalate And organic peroxides such as 1,1-bis (t-butylperoxy) cyclohexane, hydrogen peroxide and the like. When using a peroxide as a radical polymerization initiator, it can be set as a redox type initiator by combining a reducing agent. Among these, an azo compound is preferable, and especially 2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), and dimethyl-2,2'- azobis (2 -Methyl propionate).

Although the usage-amount of a polymerization initiator can be suitably selected in the range which does not impair smooth copolymerization, Usually, it is about 1 to 10 weight% with respect to the total amount of a monomer (all monomer components) and a polymerization initiator, Preferably it is about 2 to 8 weight%. .

Copolymerization can be performed by the conventional method used when manufacturing a styrene polymer or an acrylic polymer, such as solution polymerization, block polymerization, suspension polymerization, block-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the polymerization initiator may be collectively supplied to the reaction system, respectively, or a part or all of them may be added dropwise to the reaction system. For example, a method in which a solution obtained by dissolving a polymerization initiator in a polymerization solvent is added dropwise into a mixed solution of a monomer and a polymerization solvent maintained at a constant temperature, and a solution in which the monomer and the polymerization initiator are dissolved in a polymerization solvent in advance is fixed. The method of dripping and superposing | polymerizing in the polymerization solvent hold | maintained at temperature (dropping polymerization method), etc. can be used.

The polymerization solvent can be appropriately selected depending on the monomer composition and the like. As the polymerization solvent, for example, ether (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono Or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono Linear ethers such as glycol ethers such as di, trialkyl ethers, cyclic ethers such as tetrahydrofuran and dioxane, esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, 3- methoxy methyl propionate, ethyl ethoxy propionate, the 3-, C _{5 -6} cycloalkane diol mono- or di-acetate, _5- C Carboxylic acid esters such as ₆ cycloalkanedimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol mono Alkyl ether acetates, propylene glycol mono or diacetates, dipropylene glycol monoalkyl ether acetates, dipropylene glycol mono or diacetates, 1,3-propanediol monoalkyl ether acetates, 1,3-propanediol mono or diacetates, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono or di-C _{1 -4} Glycol acetate or monoacetate, tripropylene glycol monoalkyl ether acetate, glycol acetate such as tripropylene glycol mono or diacetate, or glycol ether acetate, etc.), ketone (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexa) Paddy, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amide (N, N-dimethylacetamide, N, N-dimethylformamide, etc.), sulfoxide (dimethyl sulfoxide, etc.), alicyclic alcohols, such as (methanol, ethanol, propanol, C _{5 -6} cycloalkane diols, C _{5 -6} cycloalkanediyl methanol, etc.), hydrocarbons (benzene, toluene, aliphatic hydrocarbons, aromatic hydrocarbons, such as cyclohexane, hexane, xylene, etc. Formula hydrocarbons, etc.), these mixed solvents, etc. are mentioned. Polymerization temperature can be suitably selected, for example in the range of about 30-150 degreeC.

The above method produces the copolymer in the present invention. The number average molecular weight of the copolymer is, for example, 3000 to 50000, preferably 3500 to 40000, more preferably about 4000 to 30000. Dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of a copolymer is about 1-3.

The polymerization liquid obtained by the said method can be used as curable resin composition by adjusting solid content concentration as needed, performing solvent substitution, or performing a filtration process, adding an appropriate additive or solvent suitable for a use to this. Moreover, the polymer produced | generated by superposition | polymerization can be refine | purified by precipitation, reprecipitation, etc., and this refined polymer can also be used as curable resin composition by dissolving in a solvent, such as a solvent for resist, with the said suitable additive.

Curable Resin Composition

An important feature of the curable resin composition of the present invention is that the boiling point at atmospheric pressure (0.101 MPa) contains an organic solvent having a temperature of 180 ° C or more as a solvent. Obtained by copolymerizing the copolymer, that is, a monomer mixture containing a polymerizable unsaturated compound having an alkali-soluble group and a polymerizable unsaturated compound containing a specific amount of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring. When the copolymer is dissolved in propylene glycol monomethyl ether or the like which is generally preferred as a solvent for a resist, applied to the substrate or the substrate by a slit coating method or an ink jet method, and cured to form a film, the coating film is partially formed. The problem is that the thickness is different or the coating defect occurs. However, as in the present invention, such a problem does not occur when the copolymer is dissolved in the specific organic solvent and applied to the substrate or the substrate by the slit coating method or the inkjet method. Although the reason is not necessarily clear, when the organic solvent which has a boiling point of 180 degreeC or more at normal pressure not only has a slow drying rate, but also generally contains a high viscosity and relatively high molecular weight, it contains a certain amount of hetero atoms, such as an oxygen atom. Slit through which a composition passes through a narrow flow path because it shows good affinity for a polymer having a 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane skeleton and improves the stability of the system. Even in the case of coating by a coating method or an inkjet method, it is considered that the non-uniformity of the composition, the precipitation of the polymer, the separation, and the like are less likely to occur during and after application.

Examples of the organic solvent having a boiling point of 180 ° C. or higher at atmospheric pressure include glycols (including trivalent or higher alcohols), glycol ethers, glycol ether esters, glycol esters, ketones, and the like, and more specifically, for example C _{5 -6} cycloalkane diols, C _{5 -6} cycloalkanediyl methanol, C _{5 -6} cycloalkane diol mono- or di-acetates, C _{5 -6} cycloalkanediyl methanol mono- or di-acetate, propylene glycol monomethyl or Dia Reel ether, dipropylene glycol mono-C _{1 -4} alkyl ether, dipropylene glycol C _{2 -4-alkyl} ether, dipropylene glycol mono-C _{1 -4} alkyl ether acetates, tripropylene glycol mono- or di-C _{1 -4} alkyl ethers, propylene glycol diacetate, 1,3-propanediol di-C _{3 -4} alkyl ethers, 1,3-propanediol mono-C _{2 -4} alkyl ether acetates, 1,3-propanediol mono- or diacetate, 1,3-butanediol mono- or di-C _{3 -4} alkyl ether, 1,3-butanediol mono C _{2 -4} alkyl ether acetates, 1,3-butanediol mono- or diacetate, 1,4-butanediol mono- or di-C _{3 - 4-alkyl} ethers, 1,4-butanediol mono C _{2 -4} alkyl ether acetates, 1,4-butanediol mono- or diacetate, glycerol mono-, di- or tri- C _{1 -4} alkyl ethers, glycerol mono-, di- or triacetate, glycerin mono- or di-C _{1 -4} alkyl ether di- or mono-acetate, 3,5,5-trimethyl-2-cyclohexen-1-one, diethylene glycol mono-C _{2 -4} alkyl ether, diethylene glycol mono-C _{2 -4} Alkyl ether acetates and the like. These organic solvents can be used individually or in combination of 2 or more.

As the C _{5 -6} cycloalkane diols may be mentioned the cyclopentane diol, cyclohexane diol. C _{-6 5} as cycloalkanediyl methanol may be mentioned the cyclopentane dimethanol, cyclohexane dimethanol. C _{-6 5} cycloalkane diol as a mono- or di-acetate, it may be mentioned the cyclopentane diol monoacetate, diacetate cyclopentane diol, cyclohexane diol monoacetate, cyclohexane diol diacetate. C _{-6 5} cycloalkanediyl methanol as mono- or di-acetate, it may be mentioned the cyclopentane dimethanol monoacetate, cyclopentane dimethanol diacetate, cyclohexane dimethanol monoacetate, cyclohexane dimethanol diacetate.

As propylene glycol mono or diaryl ether, propylene glycol monophenyl ether, propylene glycol diphenyl ether, etc. are mentioned, for example.

Di-propylene glycol mono-a C _{1 -4} alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether and the like. As dipropylene glycol di C _2-4 alkyl ether, for example, dipropylene glycol diethyl ether, dipropylene glycol dipropyl ether, dipropylene glycol dibutyl ether, dipropylene glycol ethylpropyl ether, dipropylene glycol ethylbutyl ether And dipropylene glycol propyl butyl ether. Di-propylene glycol mono-C _{1 -4} as alkyl ether acetate, and the like, for example dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate Can be.

Tripropylene glycol mono- or di-C _{1 -4} alkyl ethers as, for example, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dimethyl ether Tripropylene glycol diethyl ether, tripropylene glycol dipropyl ether, tripropylene glycol dibutyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl propyl ether, tripropylene glycol methyl butyl ether, tripropylene glycol ethyl propyl ether, Tripropylene glycol ethyl butyl ether, tripropylene glycol propyl butyl ether, etc. are mentioned.

1,3-propanediol di-C as a _{3 -4} alkyl ethers, for example, and the like 1,3-propanediol dipropyl ether, 1,3-propanediol dibutyl ether, 1,3-propanediol propyl butyl ether Can be. 1,3-propanediol monomethyl ether acetate as a C _{2 -4} alkyl, for example, 1,3-propanediol monoethyl ether acetate, 1,3-propanediol monopropyl ether acetate, 1,3-propanediol monobutyl ether Acetate and the like.

1,3-butanediol mono- or di-C _3-4 alkyl ethers as, for example, 1,3-butanediol monopropyl ether, 1,3-butanediol monobutyl ether, 1,3-butanediol dipropyl ether, 1,3- Butanediol dibutyl ether, 1,3-butanediolpropylbutyl ether, and the like. 1,3-butanediol mono C _{2 -4} as alkyl ether acetate, and the like, for example 1,3-butanediol monoethyl ether acetate, 1,3-butanediol monopropyl ether acetate, 1,3-butanediol monobutyl ether acetate Can be.

1,4-butanediol mono- or di-C _3-4 alkyl ethers as, for example, 1,4-butanediol monopropyl ether, 1,4-butanediol monobutyl ether, 1,4-butanediol dipropyl ether, 1,4- Butanediol dibutyl ether, 1, 4- butanediol propylbutyl ether, etc. are mentioned. 1,4-butanediol mono C _{2 -4} as alkyl ether acetate, and the like, for example 1,4-butanediol monoethyl ether acetate, 1,4-butanediol monopropyl ether acetate, 1,4-butanediol monobutyl ether acetate Can be.

A glycerin mono-, di- or tri- C _{1 -4} alkyl ether includes, for example, such as glycerin monomethyl ether, glycerin monoethyl ether, glycerin monomethyl ether, glycerin monomethyl ether. Glycerol mono- or di-C _{1 -4} alkyl ether di- or mono-acetate, as, for example, glycerol monomethyl ether monoacetate, glycerol monoethyl ether monoacetate, glycerol monopropyl ether monoacetate, glycerol monobutyl ether monoacetate, glycerol monomethyl Ether diacetate, glycerin monoethyl ether diacetate, glycerin monopropyl ether diacetate, glycerin monobutyl ether diacetate, and the like.

Diethylene glycol monomethyl ether as a C _{2 -4} alkyl includes, for example, such as diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether. Diethylene glycol mono-C _{2 -4} as alkyl ether acetate includes, for example, such as diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate.

Among these organic solvents, dipropylene glycol mono- or di-C _{2 -4-alkyl} ether, dipropylene glycol mono-C _{1 -4} alkyl ether acetates, 1,3-butanediol mono- or di-C _{3 -4} alkyl ether, 1,3-butanediol mono C _{2 -4} alkyl ether acetate, and 1,3-butanediol mono or di at least one organic solvent selected from acetate are preferred, in particular dipropylene glycol mono C _{2 -4-alkyl} ether, dipropylene glycol mono-C _{1 -4} Preference is given to at least one organic solvent selected from alkyl ether acetates and 1,3-butanediol diacetate. Moreover, although the boiling point in the normal pressure of the organic solvent is 180 degreeC or more (for example, 180-280 degreeC), More preferably, it is 200 degreeC or more (for example, 200-280 degreeC), More preferably, it is 220 degreeC or more. (For example, 220 to 280 ° C).

The said organic solvent can also be used together with another organic solvent as needed. As another organic solvent, it can select from the organic solvent whose boiling point at normal pressure is less than 180 degreeC, For example, glycol ether, glycol ether ester, glycol ester, carboxylic acid alkyl ester, aliphatic ketone can be used. Can be mentioned. A typical one is illustrated below. In addition, the number in parenthesis after a compound name shows the boiling point at normal pressure.

Glycol ethers include, for example, propylene glycol monomethyl ether (120 ° C.), propylene glycol dimethyl ether (96 ° C.), diethylene glycol dimethyl ether (162 ° C.), dipropylene glycol dimethyl ether (175 ° C.), and the like. .

Examples of the glycol ether esters include ethylene glycol monoethyl ether acetate (156 ° C), propylene glycol monomethyl ether acetate (146 ° C), and 1,3-butanediol monomethyl ether acetate (= 3-methoxybutyl acetate) ( 171 ° C) and the like.

Examples of the carboxylic acid alkyl esters include isoamyl acetate (142 ° C), ethyl lactate (155 ° C), methyl 3-methoxypropionate (142 ° C), and ethyl 3-ethoxypropionate (170 ° C). Included.

Aliphatic ketones include 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, and the like.

For example, as the organic solvent having a boiling point of not less than 180 ℃ at normal pressure, glycol ethers (e.g., propylene glycol mono- or diallyl ether, dipropylene glycol mono-C _{1 -4} alkyl ether, dipropylene glycol di-C _{2 - 4-alkyl} ethers, tripropylene glycol mono- or di-C _{1 -4} alkyl ethers, 1,3-propanediol di-C _{3 -4} alkyl ether, 1,3-butanediol mono- or di-C _{3 -4} alkyl ether, 1,4- butanediol mono- or di-C _{3 -4} alkyl ethers, glycerol mono-, di- or tri- C _{1 -4} alkyl ether, diethylene glycol mono-C in the case of using a _{2 -4} alkyl ether and the like), and the other glycol ether esters such as an organic solvent (Propylene glycol monomethyl ether acetate and the like), glycol esters, carboxylic acid alkyl esters and the like are preferably used.

Further, as the organic solvent having a boiling point of not less than 180 ℃ at normal pressure, glycol ether esters (for example, C _{5 -6} cycloalkanediyl methanol mono- or di-acetate, dipropylene glycol mono-C _{1 -4} alkyl ether acetate, 1, 3-propane diol mono-C _{2 -4} alkyl ether acetates, 1,3-butanediol mono C _{2 -4} alkyl ether acetates, 1,4-butanediol mono C _2-4 alkyl ether acetates, glycerol mono- or di-C _{1 -4} alkyl polyether di or mono-acetate, diethylene glycol mono-C _{2 -4} alkyl ether acetate and the like), or glycol esters (for example, C _{5 -6} cycloalkane diol mono- or di-acetates, C _{5 -6} cycloalkanediyl mono methanol Or diacetate, propylene glycol diacetate, 1,3-propanediol mono or diacetate, 1,3-butanediol mono or diacetate, 1,4-butanediol mono or diacetate, When using glycerin mono, di or triacetate, etc., it is preferable to use in combination with glycol ethers (dipropylene glycol dimethyl ether etc.) as another organic solvent.

The organic solvent whose boiling point in normal pressure is 180 degreeC or more can be used as a polymerization solvent, it can also be used as a solvent in curable resin composition as it is, and can also be used in order to melt a polymer at the time of manufacture of curable resin composition. In addition, when using together another organic solvent, the said other organic solvent can be used as a polymerization solvent, can also be used as a solvent in curable resin composition as it is, and can also be used in order to melt | dissolve a polymer at the time of manufacture of curable resin composition, The former is often the case.

In the present invention, the total amount of the organic solvent having a boiling point of 180 ° C. or higher at normal pressure is preferably 10% by weight or more, more preferably 15% by weight or more, and even more preferably 50% by weight with respect to the whole organic solvent in the curable resin composition. % Or more (especially 80 weight% or more). The organic solvent in the curable resin composition of this invention may be comprised only with the organic solvent whose boiling point in normal pressure is 180 degreeC or more substantially. The total amount of the organic solvent in curable resin composition is 10-99 weight% normally with respect to the whole curable resin composition, Preferably it is about 50-90 weight%.

An appropriate additive can be added to curable resin composition according to a use. Examples of such additives include photoacid generators, crosslinking agents, resins, colorants, polymerization initiators (photocationic polymerization initiators, thermal cationic polymerization initiators, and the like), antioxidants, dissolution inhibitors, sensitizers, ultraviolet absorbers, light stabilizers, adhesion improving agents, and the like. Although it is possible, it is not limited to these. When using curable resin composition as a radiation sensitive resin composition or a photosensitive resin composition, the quinonediazide compound is added in many cases. As a quinonediazide compound, the compound normally used for a radiation sensitive resin composition and the photosensitive resin composition can be used. The amount of the quinonediazide compound is, for example, 2 to 100% by weight, preferably 5 to 40% by weight, based on the solid content of the curable resin composition.

Although the curable resin composition of this invention can be used also when forming a coating film by the spray method, the roll coating method, the spin coating method, etc., it is especially useful when forming a coating film by the slit coating method or the inkjet method which pass through a narrow flow path. . Since the curable resin composition of this invention provides the film excellent in the characteristics, such as hardness, transparency, heat resistance, and heat discoloration, by hardening, it forms protective films, interlayer insulation films, etc., such as a liquid crystal display element, an integrated circuit element, and a solid-state image sensor, etc. It can use suitably as curable resin composition for following.

[Formation of Cured Coating Film]

In the formation method of the cured coating film of this invention, after coating curable resin composition of this invention on a board | substrate or a base material by the slit coating method or the inkjet method, and forming a coating film, a coating film is hardened. Examples of the substrate or substrate include glass, ceramics, silicon wafers, metals, plastics, and the like. Application | coating by the slit coating method and the inkjet method can be performed by a well-known method. When using curable resin composition as a radiation sensitive resin composition or photosensitive resin composition, after apply | coating curable resin composition on a board | substrate or a base material, it is desired by exposing radiation (light) to a coating film through a predetermined mask, and then developing. A pattern is formed. Light of various wavelengths, for example, ultraviolet rays, X-rays, and the like can be used for exposure, and g-rays, i-rays, excimer lasers, etc. are used for semiconductor resists and the like. As a developing solution, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, can be used.

Curing of a coating film is performed by heat or light. Although the thickness of the coating film (protective film, interlayer insulation film, character, pattern, etc.) after hardening can be suitably selected according to a use, it is generally 0.1-20 micrometers, Preferably it is about 0.3-10 micrometers.

Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples. In addition, the number in parenthesis after a compound name shows the boiling point at normal pressure. Dispersion degree is a value of weight average molecular weight Mw / number average molecular weight Mn.

Synthesis Example 1

A proper amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to prepare a nitrogen atmosphere, and 275 parts by weight of dipropylene glycol dimethyl ether (175 ° C.) was added and heated to 70 ° C. while stirring. Next, in the flask, 55 parts by weight of methacrylic acid (MAA), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 180 parts by weight of a mixture of ^2,6 ] decane-8-ylacrylate [50:50 (molar ratio)] (E-DCPA), and 70 parts by weight of N-cyclohexylmaleimide (CHMI) 170 parts by weight of dipropylene glycol dimethyl ether The solution dissolved in the portion was added dropwise over about 4 hours using a dropping pump. On the other hand, the solution which melt | dissolved 30 weight part of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 weight part of dipropylene glycol dimethyl ether was dripped over about 4 hours using the other dropping pump. . After completion of the dropping of the polymerization initiator, the mixture was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 30.3 wt% and an acid value of 35.7 mg-KOH / g. The acid value of the produced copolymer was 118 mg-KOH / g, the weight average molecular weight Mw was 9000, and dispersion degree was 1.80.

Synthesis Example 2

A proper amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to prepare a nitrogen atmosphere, and 345 parts by weight of dipropylene glycol dimethyl ether (175 ° C.) was added and heated to 70 ° C. while stirring. Then, in the flask, 76 parts by weight of methacrylic acid (MAA), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 A solution of 303 parts by weight of a mixture of ^2,6 ] decane-8-ylacrylate [50:50 (molar ratio)] (E-DCPA) in 220 parts by weight of dipropylene glycol dimethyl ether was added by a dropping pump for about 4 hours. It was dripped over. On the other hand, the solution which melt | dissolved 70 weight part of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 293 weight part of dipropylene glycol dimethyl ether was dripped over about 4 hours using the other dropping pump. . After completion of the dropping of the polymerization initiator, the mixture was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 29.0 wt% and an acid value of 37.9 mg-KOH / g. The acid value of the produced copolymer was 131 mg-KOH / g, the weight average molecular weight Mw was 10000, and the dispersion degree was 1.67.

Synthesis Example 3

A proper amount of nitrogen was flowed into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to prepare a nitrogen atmosphere, and 275 parts by weight of dipropylene glycol dimethyl ether (175 ° C.) was added and heated to 70 ° C. while stirring. Next, in the flask, 55 parts by weight of methacrylic acid (MAA), 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] 180 parts by weight of a mixture of decan-8-yl acrylate [50:50 (molar ratio)] (E-DCPA) and 70 parts by weight of styrene dissolved in 170 parts by weight of dipropylene glycol dimethyl ether were added dropwise pump Was dripped over about 4 hours. On the other hand, the solution which melt | dissolved 30 weight part of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 225 weight part of dipropylene glycol dimethyl ether was dripped over about 4 hours using the other dropping pump. . After completion of the dropping of the polymerization initiator, the mixture was maintained at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer solution having a solid content of 30.3 wt% and an acid value of 35.7 mg-KOH / g. The acid value of the produced copolymer was 118 mg-KOH / g, the weight average molecular weight Mw was 8500, and the dispersion degree was 1.64.

Synthesis Example 4

The same operation as in Synthesis Example 1 was performed except that the solvent used was changed to 1,3-butanediol diacetate (232 ° C) from dipropylene glycol dimethyl ether. As a result, a copolymer solution having a solid content of 30.3 wt% and an acid value of 35.7 mg-KOH / g was obtained. The acid value of the produced copolymer was 118 mg-KOH / g, the weight average molecular weight Mw was 10000, and the dispersion degree was 1.70.

Synthesis Example 5

The same operation as in Synthesis Example 1 was performed except that the solvent used was changed from dipropylene glycol dimethyl ether to propylene glycol monomethyl ether (120 ° C.). As a result, a copolymer solution having a solid content of 30.3 wt% and an acid value of 35.7 mg-KOH / g was obtained. The acid value of the produced copolymer was 118 mg-KOH / g, the weight average molecular weight Mw was 7500, and the dispersion degree was 1.70.

Synthesis Example 6

The same operation as in Synthesis Example 1 was performed except that the solvent used was changed from dipropylene glycol dimethyl ether to ethylene glycol monoethyl ether (135 ° C.). As a result, a copolymer solution having a solid content of 30.3 wt% and an acid value of 35.7 mg-KOH / g was obtained. The acid value of the produced copolymer was 118 mg-KOH / g, the weight average molecular weight Mw was 9000, and dispersion degree was 1.80.

Example 1 (application by slit coating)

After diluting 100 kg of the copolymer solution obtained in Synthesis Example 1 with 20 kg of dipropylene glycol monomethyl ether acetate (213 ° C.), 4,4 ′-[1- [4- (1- (4-hydroxyphenyl) 7.5 kg of 1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate 66.7 mol%) of -1-methylethyl) phenyl] ethylidene] diphenol was dissolved, and a Millipore filter having a pore diameter of 0.22 µm was dissolved. It filtered using the curable resin composition.

After apply | coating the said curable resin composition with the slit coating on the glass substrate, it pre-baked at 80 degreeC for 5 minutes, and formed the coating film of the film thickness of 1.5 micrometers.

The predetermined pattern mask was stuck to the obtained coating film, and the ultraviolet-ray whose light intensity in 365 nm is 10 mJ / cm <^2> was irradiated for 30 second. It was then developed for 2 minutes at 25 ° C. with a tetramethylammonium hydroxide 0.12% by weight aqueous solution and then rinsed with ultrapure water for 1 minute. Unnecessary parts were removed by these operations, and the pattern of 20 micrometers x 20 micrometers was resolved. After 30-second full exposure was performed on the resolution pattern using the same exposure apparatus, the coating film was cured by heating at 200 ° C for 1 hour in a clean oven to have various properties required as a film.

Example 2 (application by ink jet)

In the same manner as in Example 1, a curable resin composition was prepared.

The coating film was formed by inkjet instead of the slit coating, and the pattern was formed in the same manner as in Example 1 except that the pattern was formed by inkjet coating without an exposure and developing step. Curing was performed.

Example 3 (Application by Slit Coating)

A curable resin composition was prepared in the same manner as in Example 1 except that the copolymer solution obtained in Synthesis Example 2 was used instead of the copolymer solution obtained in Synthesis Example 1.

Using the obtained curable resin composition, it carried out similarly to Example 1, formation of the coating film and a pattern, and hardening of the coating film.

Example 4 Application by Inkjet

A curable resin composition was produced in the same manner as in Example 1 except that the copolymer solution obtained in Synthesis Example 2 was used instead of the copolymer solution obtained in Synthesis Example 1.

Using the obtained curable resin composition, it carried out similarly to Example 2, formation of the pattern and hardening of the coating film.

Example 5 Application by Slit Coating

A curable resin composition was produced in the same manner as in Example 1 except that the copolymer solution obtained in Synthesis Example 3 was used instead of the copolymer solution obtained in Synthesis Example 1.

Using the obtained curable resin composition, it carried out similarly to Example 1, formation of the coating film and a pattern, and hardening of the coating film.

Example 6 Application by Inkjet

A curable resin composition was produced in the same manner as in Example 1 except that the copolymer solution obtained in Synthesis Example 3 was used instead of the copolymer solution obtained in Synthesis Example 1.

Using the obtained curable resin composition, it carried out similarly to Example 2, formation of the pattern and hardening of the coating film.

Example 7 Application by Slit Coating

After diluting 100 kg of the copolymer solution obtained in Synthesis Example 4 with 20 kg of 1,3-butanediol diacetate (232 ° C), 4,4 '-[1- [4- (1- (4-hydroxyphenyl) 7.5 kg of 1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate 66.7 mol%) of -1-methylethyl) phenyl] ethylidene] diphenol was dissolved, and a Millipore filter having a pore diameter of 0.22 µm was dissolved. It filtered using the curable resin composition.

Using the obtained curable resin composition, it carried out similarly to Example 1, formation of the coating film and a pattern, and hardening of the coating film.

Example 8 (Application by Ink Jet)

In the same manner as in Example 7, a curable resin composition was prepared.

Using the obtained curable resin composition, it carried out similarly to Example 2, formation of the pattern and hardening of the coating film.

Comparative Example 1 (Application by Slit Coating)

Instead of the copolymer solution obtained in Synthesis Example 1, the copolymer solution obtained in Synthesis Example 5 was used, and butyl acetate (125 ° C) instead of dipropylene glycol monomethyl ether acetate (213 ° C) as a solvent used in the preparation of the composition. Except having used, the same operation as Example 1 was performed and the curable resin composition was manufactured.

Using the obtained curable resin composition, it carried out similarly to Example 1, formation of the coating film and a pattern, and hardening of the coating film.

Comparative Example 2 (application by ink jet)

In the same manner as in Comparative Example 1, a curable resin composition was prepared.

Using the obtained curable resin composition, it carried out similarly to Example 2, formation of the pattern and hardening of the coating film.

Comparative Example 3 (Application by Slit Coating)

Instead of the copolymer solution obtained in Synthesis Example 1, the copolymer solution obtained in Synthesis Example 6 was used, and propylene glycol monomethyl ether (213 C) was used instead of dipropylene glycol monomethyl ether acetate (213 ° C) as a solvent used in the preparation of the composition. Except having used 120 degreeC), operation similar to Example 1 was performed and the curable resin composition was manufactured.

Using the obtained curable resin composition, it carried out similarly to Example 1, formation of the coating film and a pattern, and hardening of the coating film.

Comparative Example 4 (Application by Ink Jet)

In the same manner as in Comparative Example 3, a curable resin composition was prepared.

Using the obtained curable resin composition, it carried out similarly to Example 2, and formed the pattern and hardened the coating film.

Evaluation test

Physical properties, such as the coating property in an Example and a comparative example, and the cured coating film obtained by the Example and the comparative example, were evaluated by the following method. The results are shown in Table 1.

Coatability

The coating operation was repeated for 10 hours or more continuously, and the state of the coating film was visually observed, and the case where the thickness of the coating film was uniform and the coating film defect was not seen was ○, and the case where the thickness of the coating film was different or the coating film defect was partially shown was ×. .

Transparency

The transmittance | permeability of 400-800 nm was measured using the spectrophotometer (150-20 type double beam: product made by Hitachi Seisakusho) about the board | substrate with which the cured coating film was provided. (Circle) and the case below 90% were made into (circle) and the case where 90-95% of cases where minimum transmittance | permeability exceeded 95% were made into x at this time.

Heat resistance

The board | substrate after forming a pattern in the Example and the comparative example was heated in 250 degreeC clean oven for 1 hour, and the film thickness was measured. (Circle) and the case below 90% were made into the case where (circle) and 90-95% of the case where the residual film rate exceeded 95% using the residual film rate with respect to the film thickness of the patterned board | substrate.

Heat discoloration resistance

In the Example and the comparative example, the board | substrate after hardening a coating film was heated in the clean oven at 250 degreeC for 1 hour, and the transmittance | permeability was measured using the spectrophotometer similarly to the said transparency evaluation, and the change rate of the transmittance | permeability was calculated | required. (Circle) and the case where 5-10% were the case where the change rate at this time was less than 5% were made into (x) when (triangle | delta) and 10% were exceeded.

Hardness

Using the board | substrate after hardening a coating film in the Example and the comparative example, according to the 8.4.1 pencil scraping test method of JISK-5400-1990, pencil hardness was measured by the scratch of a coating film, and surface hardness was measured.

Curable resin composition of this invention can form the film (hardened coating film) which is excellent in characteristics, such as hardness, transparency, heat resistance, and heat discoloration resistance, and is excellent in storage stability. Therefore, it is especially useful when coating by the slit coating method or the inkjet method.

Claims (5)

It is a copolymer containing the monomeric unit (A) containing an alkali-soluble group, and the monomeric unit (B) corresponding to a curable group containing polymeric unsaturated compound, The ratio of the said monomeric unit (B) makes the whole monomeric unit which comprises a copolymer. 5 to 95% by weight, and at least 30% by weight of the monomer unit (B) is selected from 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compounds represented by the following formulas (1a) and (1b): Curable resin composition containing the copolymer which is a monomer unit corresponding to 1 or more types of compounds, and the organic solvent whose boiling point in normal pressure is 180 degreeC or more. <Formula 1a>

<Formula 1b>

(Wherein R ^a represents an alkyl group having 1 to 7 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, respectively, and A represents a divalent hydrocarbon group which may each include a single bond or a hetero atom) The styrene copolymer according to claim 1, wherein the copolymer is further substituted with monomer units (A) and (B) to (C) (c1) an alkyl group, and (c2) an unsaturated carboxylic acid ester represented by the following formula (2): And (c3) a monomer unit corresponding to at least one curable group-free polymerizable unsaturated compound selected from the group consisting of N-substituted maleimides. <Formula 2>

[Wherein, R ¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ² represents a primary or secondary alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group, an aralkyl group, or- (R ³ -O) represents an _m -R ⁴ group, wherein R ³ represents a divalent hydrocarbon group having 1 to 12 carbon atoms, R ⁴ represents a hydrogen atom or a hydrocarbon group, and m represents an integer of 1 or more. The 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring-containing compound represented by the formula (1a) or (1b) is a 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decane-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^{2 , 6} ] decane-9-yloxy) ethyl (meth) acrylate, or 2- (3,4-epoxytricyclo [5.2.1.0 ^{2 , 6} ] decane-8-yloxy) ethyl ( Curable resin composition which is meth) acrylate. Any one of claims 1 to A method according to any one of claim 3, wherein the organic solvent having a boiling point at normal pressure of not less than 180 ℃ C _{5 -6} cycloalkane diols, C _{5 -6} cycloalkanediyl methanol, C _{5 -6} cycloalkane diol mono or di-acetates, C _{5 -6} cycloalkanediyl methanol mono- or di-acetate, propylene glycol mono or diallyl ether, dipropylene glycol mono-C _{1 -4} alkyl ether, dipropylene glycol C _{2 -4-alkyl} ether, dipropylene glycol mono-C _{1 -4} alkyl ether acetates, tripropylene glycol mono- or di-C _{1 -4} alkyl ethers, propylene glycol diacetate, 1,3-propanediol di-C _{3 -4} alkyl ethers, 1,3-propanediol mono-C _{2 -4} alkyl ether acetates, 1,3-propanediol mono- or diacetate, 1,3-butanediol mono- or di-C _3-4 alkyl ethers, 1,3-butanediol mono C _{2 -4} alkyl ether acetates, 1,3- Butanediol mono or dia Three lactate, 1,4-butanediol mono- or di-C _{3 -4} alkyl ether, 1,4-butanediol mono C _{2 -4} alkyl ether acetates, 1,4-butanediol mono- or diacetate, glycerol mono-, di- or tri- C _{1 -4} alkyl ethers, glycerol mono-, di- or triacetate, glycerin mono- or di-C _{1 -4} alkyl ether di- or mono-acetate, 3,5,5-trimethyl-2-cyclohexen-1-one, diethylene glycol mono-C _2-4 alkyl ether, and diethylene glycol mono-C _2-4 the curable resin composition of an organic solvent at least one selected from the alkyl ether acetate. The method of forming the cured coating film which hardens a coating film after coating the curable resin composition of any one of Claims 1-4 on a board | substrate or a base material by the slit coating method or the inkjet method, and forming a coating film.